US4613681A - Process for the manufacture of fluorinated alkanols and esters thereof - Google Patents
Process for the manufacture of fluorinated alkanols and esters thereof Download PDFInfo
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- US4613681A US4613681A US06/163,978 US16397880A US4613681A US 4613681 A US4613681 A US 4613681A US 16397880 A US16397880 A US 16397880A US 4613681 A US4613681 A US 4613681A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
- C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
Definitions
- the present invention concerns a process for the preparation of 1, 1, 2, 2 - tetrahydro fluorinated alkanols and of the carboxylic acid esters of these alkanols. These products have the following general formulae:
- R F represents a straight of branched chain perfluorinated radical containing from 1 to 20 carbon atoms and R 1 represents a hydrogen atom or an aliphatic or aromatic hydrocarbon radical.
- the alcohols can also be obtained according to the process of French Pat. No. 2,096,179, which consists of preparing the nitrates R F CH 2 CH 2 ONO 2 by the reaction of the iodides R F CH 2 CH 2 I with nitric acid and of hydrogenating these nitrates in alcohol.
- This process presents the drawback of necessitating two reaction stages, the last one of which must be carried out under a high hydrogen pressure.
- French Pat. No. 2,180,113 describes a process for the production of mixtures of alcohol R F C 2 H 4 OH and of formates R F C 2 H 4 OCOH by the reaction, at high temperture, of iodides R F C 2 H 4 I with dimethyl formamide in the presence of a little bit of water.
- This process has the drawback of requiring very strict reaction conditions and of furnishing some olefin R F CH ⁇ CH 2 as a by-product which diminishes the yield accordingly.
- a good selectivity in alcohol and formate can only be obtained by using very large quantities of dimethyl formamide.
- the process of the present invention makes it possible to prepare fluorinated alkanols and/or esters from fluorinated iodides R F C 2 H 4 I in one stage at high yields.
- the present invention comprises a process for the preparation of a fluorinated compound of the following general formula:
- R F is a straight or branched chain perfluorinated radical, C n F 2n+1 , containing 1 to 20 C atoms, R is a hydrogen atom or --COR 1 , and R 1 is a hydrogen atom or an aliphatic or aromatic hydrocarbon radical.
- the peracids which can be used are, for instance, perbenzoic, para-nitroperbenzoic, chloroperbenzoic and perphthalic acid, but in general the more easily accessible aliphatic peracids are preferred, such as performic, peracetic, perpropionic or perbutyric acid.
- These peracids can be obtained according to the known preparation methods for these products.
- One of the preparation methods which is especially simple, consists in using a mixture of hydrogen peroxide and of the carboxylic acid which furnishes the percarboxylic acid according to the following balanced reaction:
- the degree of conversion, at equilibrium, of the hydrogen peroxide into performic acid amounts to 70% for a molar ratio of HCOOH/H 2 O 2 of 3, to 82% for a molar ratio of 5, and to 95% for a molar ratio of 10.
- the rate of formation of the peracid from the acid and the hydrogen peroxide depends on the nature of the acid being used and the reaction can, as a rule, be accelerated by the introduction of slight amounts of a strong acid such as H 2 SO 4 .
- a strong acid such as H 2 SO 4
- strong organic acids such as, for instance, HCOOH or CF 3 COOH
- the equilibrium can be attained rapidly without catalyst.
- the percarboxylic acids obtained by this method are perfectly suitable for the process of the invention, even if the conversion of the hydrogen peroxide into the peracid is not quantitative and if these mixtures still contain unconverted hydrogen peroxide.
- the reaction of the invention is preferably carried out in a solvent medium.
- the solvent can be either the carboxylic acid from which the peracid has been prepared (HCOOH, CH 3 COOH, CH 3 CH 2 COOH, and the like) or another solvent which is inert towards the peracids, such as aromatic hydrocarbons, halogenated solvents (CH 2 Cl 2 , CHCl 3 , dichloroethane, trichloro trifluoro ethane, and the like), certain hydrocarbons or certain ethers (dioxane), and the like.
- the reaction can be carried out by introducing the iodide R F C 2 H 4 I into the peracid, but with a view to reducing the decomposition of the peracid as much as possible, it is desirable to introduce the peracid into the iodide.
- the reaction temperature is not critical and the reaction can be carried out within a rather wide temperature range, but in general it is preferred for it to be carried out at temperatures close to the ambient temperature (15° to 45° C.)
- the iodine of the fluorinated iodide can be found at a higher degree of oxidation than that of elementary iodine, and hypoiodous and iodic acids can, in particular, be formed.
- This supplementary oxidation obviously consumes large quantities of peracids or of hydrogen peroxide, but it is possible to reduce this drawback by fixing the iodine as it is being formed.
- the fluorinated products formed are insoluble in water and can, as a rule, be separated by simple decantation after dilution of the reaction medium with water. This separation is preferably carried out after reduction of the iodinated derivatives by means of a conventional reducing agent such as sodium sulfite, for instance.
- a conventional reducing agent such as sodium sulfite, for instance.
- this solvent can be separated from the fluorinated products by any appropriate technique, for instance by distillation.
- the fluorinated esters R F C 2 H 4 OCOR 1 and the fluorinated alcohols R F C 2 H 4 OH prepared according to the present process are useful raw materials for the production of surfactants and hydrophobic and oleophobic products. These products can, in particular, be easily converted into acrylic or methacrylic esters which permit the preparation, by polymerization, of hydrophobic and oleophobic agents for textile materials, leather or paper.
- the mixtures of esters R F C 2 H 4 OCOR 1 and alcohols R F C 2 H 4 OH can likewise be converted into useful products.
- a mixture of alcohol R F C 2 H 4 OH and of formate R F C 2 H 4 OCOH can be converted into an acrylate by transesterification with methyl acrylate, for example.
- the mixture or alcohol and ester can also be entirely converted into alcohol by the hydrolysis of the ester, by saponification or by transesterification with methanol, for example.
- the resultant mixture is then added in 1 hour and 40 minutes to a mixture of 48 g of C 6 F 13 C 2 H 4 I and 20 g of formic acid, while maintaining the temperature at 40° C. during the entire operation.
- the reaction medium is still kept at 40° C. for one hour after the addition has been completed and then 100 ml of water are introduced and the medium is decolorized by the addition of sodium sulfite.
- the lower phase is then decanted and washed twice with 50 ml of water. 41 g of a product containing the following compounds are thus recovered:
- reaction mixture was analyzed by gas chromatography, after calibration with samples of the various pure products.
- This solution is then allowed to run into a mixture of 24 g of C 6 F 13 C 2 H 4 I and 20 ml of methylene chloride during a time period of 1 hour, while the temperature is maintained at 30° C.
- the reaction medium is still kept at 30° C. for 1 additional hour after the addition of the reactants has been terminated and then 50 ml of water are allowed to run in and sodium sulfite is added until complete decolorization of the iodine occurs.
- the lower phase is decanted and washed with 50 ml of water.
- the methylene chloride is then evaporated and 19 g of fluorinated product are recovered, containing:
- Example 2 is repeated except that the peracid obtained from:
- a solution of performic acid is prepared by mixing 92 g of formic acid and 10 g of 70% hydrogen peroxide, and this mixture is kept at 20° C. for 1 hour and 30 minutes. This product is then allowed to run, under agitation, into a mixture of 48 g of C 6 F 13 C 2 H 4 I and 20 g of formic acid during a time period of 2 hours, while maintaining the temperature at 25°-30° C. The mixture having been obtained is allowed to rest at 25° C. for 1 hour and then it is treated with water and sulfite. 40 g of product are obtained, containing:
- Example 2 is repeated, but the peracid solution is allowed to run into the C 6 F 13 C 2 H 4 I, while maintaining the temperature of the latter at 60° C. After treatment, 38 g of product are recovered, containing:
- Example 2 is repeated, but the C 6 F 13 C 2 H 4 I is replaced by 37.5 g of C 4 F 9 C 2 H 4 I. After treatment, 28 g of product containing the following compounds are thus obtained:
- Example 2 is repeated, with the difference of replacing the iodide having an R F containing 6 carbon atoms by 53.7 g of an R F C 2 H 4 I composed of a mixture of the various homologs of C 4 F 9 C 2 H 4 I to C 18 F 37 C 2 H 4 I of the following composition by weight:
- the mean molecular weight of this product is close to 534.
- a solution of peracetic acid is prepared by keeping a mixture of 50 g of acetic acid, 5 g of 70% hydrogen peroxide and 0.5 g of sulfuric acid at 20° C. for 2 hours and 30 minutes. The mixture having been obtained is then added to 24 g of C 6 F 13 C 2 H 4 I during a time period of 1 hour and 30 minutes, with the temperature being kept at 30° C. during the entire duration of the addition. The reaction medium is still kept at 30° C. for an additional one hour, and then it is treated with 100 ml of water and a sufficient quantity of sodium sulfite solution in order to decolorize it. After decantation and washing with water, 21 g of fluorinated product are obtained, which according to chromatographic analysis contains:
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Abstract
This invention relates to a process for the preparation of a fluorinated compound of the general formula
R.sub.F C.sub.2 H.sub.4 OR
comprising reacting an iodide of the general formula RF C2 H4 I with a percarboxylic acid of the general formula R1 CO3 H at a temperature and for a time sufficient to form said fluorinated compound; in said formulae RF is a straight or branched chain perfluorinated radical containing 1 to 20 C atoms, R is a hydrogen atom or --COR1, and R1 is a hydrogen atom or an aliphatic or aromatic hydrocarbon radical.
Description
The present invention concerns a process for the preparation of 1, 1, 2, 2 - tetrahydro fluorinated alkanols and of the carboxylic acid esters of these alkanols. These products have the following general formulae:
R.sub.F CH.sub.2 CH.sub.2 OH and
R.sub.F CH.sub.2 CH.sub.2 OCOR.sup.1
in which RF represents a straight of branched chain perfluorinated radical containing from 1 to 20 carbon atoms and R1 represents a hydrogen atom or an aliphatic or aromatic hydrocarbon radical.
Up to the present time, these products have been obtained according to the process described in French Pat. No. 1,380,579, by a reaction of the iodides, RF CH2 CH2 I, with fuming sulfuric acid, followed by a hydrolysis of the sulfates having been formed. However, this process presents the disadvantages of furnishing large quantities of sulfuric diesters which are difficult to hydrolyze. According to the process described in U.S. Pat. No. 3,239,557, it is possible to obtain the esters RF C2 H4 OCOR1 by the conventional reaction of the iodides RF C2 H4 I with salts of the carboxylic acids R1 COOH. The yields, however, are not very good, since larger or smaller quantities of olefins RF CH═CH2 are formed.
The alcohols can also be obtained according to the process of French Pat. No. 2,096,179, which consists of preparing the nitrates RF CH2 CH2 ONO2 by the reaction of the iodides RF CH2 CH2 I with nitric acid and of hydrogenating these nitrates in alcohol. This process, however, presents the drawback of necessitating two reaction stages, the last one of which must be carried out under a high hydrogen pressure.
French Pat. No. 2,180,113 describes a process for the production of mixtures of alcohol RF C2 H4 OH and of formates RF C2 H4 OCOH by the reaction, at high temperture, of iodides RF C2 H4 I with dimethyl formamide in the presence of a little bit of water. This process has the drawback of requiring very strict reaction conditions and of furnishing some olefin RF CH═CH2 as a by-product which diminishes the yield accordingly. A good selectivity in alcohol and formate can only be obtained by using very large quantities of dimethyl formamide.
The process of the present invention makes it possible to prepare fluorinated alkanols and/or esters from fluorinated iodides RF C2 H4 I in one stage at high yields.
Briefly, the present invention comprises a process for the preparation of a fluorinated compound of the following general formula:
R.sub.F C.sub.2 H.sub.4 OR
comprising reacting an iodide for the general formula RF C2 H4 I with a percarboxylic acid of the general formula R1 CO3 H at a temperature and for a time sufficient to form said fluorinated compound; in said formulae RF is a straight or branched chain perfluorinated radical, Cn F2n+1, containing 1 to 20 C atoms, R is a hydrogen atom or --COR1, and R1 is a hydrogen atom or an aliphatic or aromatic hydrocarbon radical.
With the instant process, when the iodide, RF C2 H4 I, is mixed with a peracid, R1 CO3 H, there is the immediate formation of iodine and the fluorinated compound is converted into an alkanol, RF C2 H4 OH, into an ester RF C2 H4 OCOR1, or into a mixture of the two. The relative proportions of alkanol and of ester depend principally on the particular peracid and on the operating conditions; i.e., type of solvent, water content of the reaction medium, temperature, molar ratio of the reagents, and the like. From the disclosure given herein those skilled in this art can make the adjustments necessary to obtain the particular perfluoro compounds desired.
The peracids which can be used are, for instance, perbenzoic, para-nitroperbenzoic, chloroperbenzoic and perphthalic acid, but in general the more easily accessible aliphatic peracids are preferred, such as performic, peracetic, perpropionic or perbutyric acid. These peracids can be obtained according to the known preparation methods for these products. One of the preparation methods, which is especially simple, consists in using a mixture of hydrogen peroxide and of the carboxylic acid which furnishes the percarboxylic acid according to the following balanced reaction:
R.sup.1 COOH+H.sub.2 O.sub.2 ⃡R.sup.1 CO.sub.3 H+H.sub.2 O.
Depending on the value of the ratio of R1 COOH/H2 O2, the nature of the radical R1, the quantity of water introduced with the reagents and depending on the temperature, a certain degree of conversion of the hydrogen peroxide into peracid is obtained. Thus, in the case of formic acid with 70% hydrogen peroxide at 20° C., the degree of conversion, at equilibrium, of the hydrogen peroxide into performic acid amounts to 70% for a molar ratio of HCOOH/H2 O2 of 3, to 82% for a molar ratio of 5, and to 95% for a molar ratio of 10. The rate of formation of the peracid from the acid and the hydrogen peroxide depends on the nature of the acid being used and the reaction can, as a rule, be accelerated by the introduction of slight amounts of a strong acid such as H2 SO4. In the case of strong organic acids such as, for instance, HCOOH or CF3 COOH, the equilibrium can be attained rapidly without catalyst. The percarboxylic acids obtained by this method are perfectly suitable for the process of the invention, even if the conversion of the hydrogen peroxide into the peracid is not quantitative and if these mixtures still contain unconverted hydrogen peroxide.
The peracids obtained by any other process can likewise be used for the present invention.
The reaction of the invention is preferably carried out in a solvent medium. The solvent can be either the carboxylic acid from which the peracid has been prepared (HCOOH, CH3 COOH, CH3 CH2 COOH, and the like) or another solvent which is inert towards the peracids, such as aromatic hydrocarbons, halogenated solvents (CH2 Cl2, CHCl3, dichloroethane, trichloro trifluoro ethane, and the like), certain hydrocarbons or certain ethers (dioxane), and the like.
The reaction can be carried out by introducing the iodide RF C2 H4 I into the peracid, but with a view to reducing the decomposition of the peracid as much as possible, it is desirable to introduce the peracid into the iodide. The reaction temperature is not critical and the reaction can be carried out within a rather wide temperature range, but in general it is preferred for it to be carried out at temperatures close to the ambient temperature (15° to 45° C.)
Depending on the quantities of peracid utilized the iodine of the fluorinated iodide can be found at a higher degree of oxidation than that of elementary iodine, and hypoiodous and iodic acids can, in particular, be formed. This supplementary oxidation obviously consumes large quantities of peracids or of hydrogen peroxide, but it is possible to reduce this drawback by fixing the iodine as it is being formed. Out of the methods making it possible to fix the iodine consists of carrying out the reaction in the presence of an aromatic hydrocarbon capable of being iodinated, such as benzene, toluene, or xylene which is partially converted into an iodinated aromatic derivative according to the reaction: ##STR1##
The fluorinated products formed are insoluble in water and can, as a rule, be separated by simple decantation after dilution of the reaction medium with water. This separation is preferably carried out after reduction of the iodinated derivatives by means of a conventional reducing agent such as sodium sulfite, for instance. When the reaction is carried out in the presence of a solvent which is immisicible with water, then this solvent can be separated from the fluorinated products by any appropriate technique, for instance by distillation.
The conversion of the iodide RF C2 H4 I into alcohols and esters takes place with excellent selectivities and the formation of by-products has not been observed. In particular, very little olefin RF CH═CH2 is formed. This is a by-product which, as a rule, is formed in large quantities during the course of most of the other production processes and which lowers their yields considerably.
The fluorinated esters RF C2 H4 OCOR1 and the fluorinated alcohols RF C2 H4 OH prepared according to the present process are useful raw materials for the production of surfactants and hydrophobic and oleophobic products. These products can, in particular, be easily converted into acrylic or methacrylic esters which permit the preparation, by polymerization, of hydrophobic and oleophobic agents for textile materials, leather or paper. The mixtures of esters RF C2 H4 OCOR1 and alcohols RF C2 H4 OH can likewise be converted into useful products. Thus, a mixture of alcohol RF C2 H4 OH and of formate RF C2 H4 OCOH can be converted into an acrylate by transesterification with methyl acrylate, for example. The mixture or alcohol and ester can also be entirely converted into alcohol by the hydrolysis of the ester, by saponification or by transesterification with methanol, for example.
The invention will be further described in connection with the following examples which are given for purposes of illustration only.
12 g of C6 F13 C2 H4 I (0.025 moles) are introduced into a reactor containing 7.9 g of para-nitroperbenzoic acid (0.043 moles) and 50 ml of methylene chloride, while maintaining the temperature between 25° and 30° C. by external cooling with cold water. The mixture is kept at this temperature, under agitation, for 3 hours. 100 ml of water are then introduced and the liquid phase is analyzed by gas chromatography, Besides methylene chloride, the liquid phase contains a mixture of C6 F13 C2 H4 OH and of C6 F13 C2 H4 I in the following proportions:
C6 F13 C2 H4 OH: 52%
C6 F13 C2 H4 I: 48%
92 g of formic acid, 10 g of 70% hydrogen peroxide, and 1 g of sulfuric acid are introduced into an agitated reactor and this mixture is kept under agitation for 1 hour at 20° C. for the purpose of preparing some performic acid.
The resultant mixture is then added in 1 hour and 40 minutes to a mixture of 48 g of C6 F13 C2 H4 I and 20 g of formic acid, while maintaining the temperature at 40° C. during the entire operation. The reaction medium is still kept at 40° C. for one hour after the addition has been completed and then 100 ml of water are introduced and the medium is decolorized by the addition of sodium sulfite. The lower phase is then decanted and washed twice with 50 ml of water. 41 g of a product containing the following compounds are thus recovered:
1%--C6 F13 C2 H4 OH
44%--C6 F13 C2 H4 I
53%--C6 F13 C2 H4 OCOH
The reaction mixture was analyzed by gas chromatography, after calibration with samples of the various pure products.
46 g of formic acid, 5 g of 70% hydrogen peroxide and 0.5 g of sulfuric acid are introduced into an agitated reactor and this mixture is kept under agitation for one hour at 20° C.
This solution is then allowed to run into a mixture of 24 g of C6 F13 C2 H4 I and 20 ml of methylene chloride during a time period of 1 hour, while the temperature is maintained at 30° C. The reaction medium is still kept at 30° C. for 1 additional hour after the addition of the reactants has been terminated and then 50 ml of water are allowed to run in and sodium sulfite is added until complete decolorization of the iodine occurs. The lower phase is decanted and washed with 50 ml of water. The methylene chloride is then evaporated and 19 g of fluorinated product are recovered, containing:
3%--C6 F13 C2 H4 OH
35%--C6 F13 C2 H4 I
58%--C6 F13 C2 H4 OCOH
Example 2 is repeated except that the peracid obtained from:
HCOOH: 92 g
70% H2 O2 : 10 g
H2 SO4 : 1 g
is introduced into a mixture of:
C6 F13 C2 H4 I: 24 g
HCOOH: 20 g.
After treatment, 19 g of product containing the following compounds are obtained:
C6 F13 CH═CH2 : 0.1%
C6 F13 C2 H4 OH: 2.6%
C6 F13 C2 H4 I: 15%
C6 F13 C2 H4 OCOH: 80%
A solution of performic acid is prepared by mixing 92 g of formic acid and 10 g of 70% hydrogen peroxide, and this mixture is kept at 20° C. for 1 hour and 30 minutes. This product is then allowed to run, under agitation, into a mixture of 48 g of C6 F13 C2 H4 I and 20 g of formic acid during a time period of 2 hours, while maintaining the temperature at 25°-30° C. The mixture having been obtained is allowed to rest at 25° C. for 1 hour and then it is treated with water and sulfite. 40 g of product are obtained, containing:
C6 F13 C2 H4 OH: 7%
C6 F13 C2 H4 I: 14.8%
C6 F13 C2 H4 OCOH: 76.5%
Example 2 is repeated, but the peracid solution is allowed to run into the C6 F13 C2 H4 I, while maintaining the temperature of the latter at 60° C. After treatment, 38 g of product are recovered, containing:
C6 F13 C2 H4 OH: 1.3%
C6 F13 C2 H4 I: 35%
C6 F13 C2 H4 OCOH: 62%
Example 2 is repeated, but the C6 F13 C2 H4 I is replaced by 37.5 g of C4 F9 C2 H4 I. After treatment, 28 g of product containing the following compounds are thus obtained:
C4 F9 C2 H4 OH: 2%
C4 F9 C2 H4 I: 36%
C4 F9 C2 H4 OCOH: 60%
Example 2 is repeated, with the difference of replacing the iodide having an RF containing 6 carbon atoms by 53.7 g of an RF C2 H4 I composed of a mixture of the various homologs of C4 F9 C2 H4 I to C18 F37 C2 H4 I of the following composition by weight:
C4 F9 C2 H4 I: 0.9%
C6 F13 C2 H4 I: 51%
C8 F17 C2 H4 I: 28.2%
C10 F21 C2 H4 I: 11.5%
C12 F25 C2 H4 I: 4.4%
C14 F29 C2 H4 I: 1.7%
C16 F33 C2 H4 I: 0.6%
C18 F37 C2 H4 I: 0.2%
The mean molecular weight of this product is close to 534.
After reaction and treatment as indicated in Example 2, 45 g of product are obtained, containing approximately:
RF C2 H4 OH: 2%
RF C2 H4 I: 50%
RF C2 H4 OCOH: 46%
A solution of peracetic acid is prepared by keeping a mixture of 50 g of acetic acid, 5 g of 70% hydrogen peroxide and 0.5 g of sulfuric acid at 20° C. for 2 hours and 30 minutes. The mixture having been obtained is then added to 24 g of C6 F13 C2 H4 I during a time period of 1 hour and 30 minutes, with the temperature being kept at 30° C. during the entire duration of the addition. The reaction medium is still kept at 30° C. for an additional one hour, and then it is treated with 100 ml of water and a sufficient quantity of sodium sulfite solution in order to decolorize it. After decantation and washing with water, 21 g of fluorinated product are obtained, which according to chromatographic analysis contains:
C6 F13 CH═CH2 : 0.8%
C6 F13 C2 H4 OH: 15%
C6 F13 C2 H4 I: 45%
C6 F13 C2 H4 OCOH: 37%
While the invention has been described in connection with a preferred embodiment, it is not intended to limit the scope of the invention to the particular form set forth, but, on the contrary, it is intended to cover such alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A process for the preparation of a fluorinated alkanol, ester, or mixture thereof of the general formula
R.sub.F C.sub.2 H.sub.4 OR
comprising reacting an iodide of the general formula RF C2 H4 I with a percarboxylic acid of the general formula R1 CO3 H at a temperature and for a time sufficient to form said fluorinated compound; in said formulae RF is a straight or branched chain perfluorinated radical containing 1 to 20 C atoms, R is a hydrogen atom or --COR1, and R1 is a hydrogen atom or an aliphatic or aromatic hydrocarbon radical.
2. The process of claim 1 in which the reaction is carried out in the presence of a solvent for said perfluorinated compound which is inert to the peracid.
3. The process of claims 1 or 2 in which the iodide is added to the percarboxylic acid.
4. The process of claims 1 or 2 in which the percarboxylic acid is added to the iodide.
5. The process of claims 1 or 2 in which the temperature is from about 15° to 45° C.
6. The process of claims 1 or 2 in which the percarboxylic acid is an aliphatic peracid selected from performic, peracetic, perpropionic, or perbutyric acid.
7. The process of claims 1 or 2 in which an aromatic hydrocarbon capable of being iodinated is added to the reaction mixture to fix iodine released during the reaction.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7920280A FR2463113A1 (en) | 1979-08-08 | 1979-08-08 | PROCESS FOR THE PREPARATION OF 1,1,2,2, TETRAHYDRO PERFLUORO ALCANOLS AND ESTERS OF SUCH ALCOHOLS |
| FR7920280 | 1979-08-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4613681A true US4613681A (en) | 1986-09-23 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/163,978 Expired - Lifetime US4613681A (en) | 1979-08-08 | 1980-06-30 | Process for the manufacture of fluorinated alkanols and esters thereof |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4613681A (en) |
| EP (1) | EP0024224B1 (en) |
| JP (1) | JPS5629532A (en) |
| BR (1) | BR8004957A (en) |
| DE (1) | DE3060448D1 (en) |
| FR (1) | FR2463113A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4968848A (en) * | 1988-02-23 | 1990-11-06 | Hoechst Aktiengesellschaft | Process of the prparation of perfluoroalkyl compounds, and pentafluoroethyltrimethylsilane |
| US5202506A (en) * | 1992-04-02 | 1993-04-13 | E. I. Du Pont De Nemours And Company | Oxidative drown process for 2-perfluoroalkylethyl alcohols |
| US20040045387A1 (en) * | 2002-09-06 | 2004-03-11 | Visteon Global Technologies, Inc. | Barrel-shaped pinion |
| US20070232766A1 (en) * | 2004-04-26 | 2007-10-04 | Takeomi Hirasaka | Method for Producing Fluorine-Containing Acrylic Ester |
| US20070244338A1 (en) * | 2004-04-26 | 2007-10-18 | Yoshio Funakoshi | Method for Producing Fluorine-Containing Acrylic Ester |
| US20070277951A1 (en) * | 2004-02-06 | 2007-12-06 | Westerkamp Arved H | Modularly Constructed Paper Machine Covering |
| US20080021184A1 (en) * | 2004-04-26 | 2008-01-24 | Yoshio Funakoshi | Method For Producing Fluorine-Containing (Meth)Acrylic Ester |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO165188C (en) * | 1986-12-22 | 1991-01-09 | Atochem | SYNTHESIS OF 1,1,2,2-TETRAHYDROPERFLUORAL CHANNELS AND THEIR ESTERS. |
| NO166122C (en) * | 1986-12-22 | 1991-06-05 | Atochem | PROCEDURE FOR THE PREPARATION OF A MIXTURE OF 1,1,2,2-TETRAHYDROPERFLUORAL CHANOLS AND THEIR ESTERS. |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3171861A (en) * | 1957-06-11 | 1965-03-02 | Minnesota Mining & Mfg | Fluorinated aliphatic alcohols |
| US3812008A (en) * | 1970-05-20 | 1974-05-21 | E Fryer | Seal ring for nuclear reactors |
| US3824296A (en) * | 1970-06-10 | 1974-07-16 | Hoechst Ag | Process for the manufacture of 1,1,2,2-tetrahydro-perfluoro-alkanols |
| US4001309A (en) * | 1973-04-16 | 1977-01-04 | Asahi Glass Co., Ltd. | Method of preparing polyfluoroalkyl group containing compounds |
| US4219681A (en) * | 1978-08-09 | 1980-08-26 | Hoechst Aktiengesellschaft | Process for the manufacture of 2-(perfluoroalkyl)-ethanols |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3182008A (en) * | 1961-06-14 | 1965-05-04 | Union Carbide Corp | Hydroxylation of organic compounds |
| DE2318677A1 (en) * | 1973-04-13 | 1974-11-07 | Hoechst Ag | 2-Perfluoro-alkyl-ethyl alcohols - by saponification of corresp iodides in non-oxidising oxygen acids or hydrogen iodide |
-
1979
- 1979-08-08 FR FR7920280A patent/FR2463113A1/en active Granted
-
1980
- 1980-06-30 US US06/163,978 patent/US4613681A/en not_active Expired - Lifetime
- 1980-07-25 EP EP80401108A patent/EP0024224B1/en not_active Expired
- 1980-07-25 DE DE8080401108T patent/DE3060448D1/en not_active Expired
- 1980-08-07 BR BR8004957A patent/BR8004957A/en unknown
- 1980-08-08 JP JP10838980A patent/JPS5629532A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3171861A (en) * | 1957-06-11 | 1965-03-02 | Minnesota Mining & Mfg | Fluorinated aliphatic alcohols |
| US3812008A (en) * | 1970-05-20 | 1974-05-21 | E Fryer | Seal ring for nuclear reactors |
| US3824296A (en) * | 1970-06-10 | 1974-07-16 | Hoechst Ag | Process for the manufacture of 1,1,2,2-tetrahydro-perfluoro-alkanols |
| US4001309A (en) * | 1973-04-16 | 1977-01-04 | Asahi Glass Co., Ltd. | Method of preparing polyfluoroalkyl group containing compounds |
| US4219681A (en) * | 1978-08-09 | 1980-08-26 | Hoechst Aktiengesellschaft | Process for the manufacture of 2-(perfluoroalkyl)-ethanols |
Non-Patent Citations (2)
| Title |
|---|
| Journal of the American Chemical Society, Jul. 19, 1978, pp. 4888 and 4889. * |
| Journal of the Chemical Society, Chemical Communications, vol. 21, Nov. 1, 1978, p. 919. * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4968848A (en) * | 1988-02-23 | 1990-11-06 | Hoechst Aktiengesellschaft | Process of the prparation of perfluoroalkyl compounds, and pentafluoroethyltrimethylsilane |
| US5202506A (en) * | 1992-04-02 | 1993-04-13 | E. I. Du Pont De Nemours And Company | Oxidative drown process for 2-perfluoroalkylethyl alcohols |
| US20040045387A1 (en) * | 2002-09-06 | 2004-03-11 | Visteon Global Technologies, Inc. | Barrel-shaped pinion |
| US20070277951A1 (en) * | 2004-02-06 | 2007-12-06 | Westerkamp Arved H | Modularly Constructed Paper Machine Covering |
| US20070232766A1 (en) * | 2004-04-26 | 2007-10-04 | Takeomi Hirasaka | Method for Producing Fluorine-Containing Acrylic Ester |
| US20070244338A1 (en) * | 2004-04-26 | 2007-10-18 | Yoshio Funakoshi | Method for Producing Fluorine-Containing Acrylic Ester |
| US20080021184A1 (en) * | 2004-04-26 | 2008-01-24 | Yoshio Funakoshi | Method For Producing Fluorine-Containing (Meth)Acrylic Ester |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2463113A1 (en) | 1981-02-20 |
| JPS6157813B2 (en) | 1986-12-09 |
| EP0024224B1 (en) | 1982-05-19 |
| DE3060448D1 (en) | 1982-07-08 |
| BR8004957A (en) | 1981-02-17 |
| EP0024224A1 (en) | 1981-02-25 |
| FR2463113B1 (en) | 1984-02-17 |
| JPS5629532A (en) | 1981-03-24 |
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